Tetrahydroindazoles with a phenyl ether structures, herbicidal compositions and use

ABSTRACT

N-(Phenyl)-tetrahydroindazole derivatives of the general formula Ia and Ib ##STR1## where R 1  is halogen; 
     R 2  C 1  -C 6  -alkoxycarbonyl-C 3  -C 5  -alkenyl or C 1  -C 3  -alkyl which is substituted in the 1- or 2-position by C 1  -C 6  -alkoxycarbonyl or a 5-or 6-membered saturated or monounsaturated heterocycle which contains one oxygen or sulfur as heteroatom and can be substituted by rom one to four C 1  -C 4  -alkyls, and 
     R 3  is C 2  -C 7  -alkyl, C 3  -C 6  -C 3  -C 6  -alkynyl, C 1  -C 6  -alkoxycarbonyl-C 3  -C 5  -alkenyl or C 1  -C 3  -alkyl which is substituted in the 1-or 2-position by C 1  -C 6  -alkoxycarbonyl or a 5- or 6-membered saturated or monounsaturated heterocycle which contains one oxygen or sulfur as heteroatom and can be substituted by from one to four C 1  -C 4  -alkyls, 
     their manufacture and their use.

This application is a division of application Ser. No. 07/457,973 filedon Dec. 27, 1989 now U.S. Pat. No. 4,997,472.

The present invention relates to novel N-phenyltetrahydroindazolederivatives of the general formulae Ia and Ib ##STR2## where R¹ ishalogen,

R² is C₁ -C₆ -alkoxycarbonyl-C₃ -C₅ -alkenyl or C₁ -C₃ -alkyl which issubstituted in the 1 or 2 position by C₁ -C₆ -alkoxycarbonyl or a 5- or6-membered saturated or monounsaturated heterocycle which contains oneoxygen or sulfur as heteroatom and can be substituted by one to four C₁-C₄ -alkyls, and

R³ is C₂ -C₇ -alkyl, C₃ -C₆ -alkenyl, C₃ -C₆ -alkynyl, C₁ -C₆-alkoxycarbonyl-C₃ -C₅ -alkenyl or C₁ -C₃ -alkyl which is substituted inthe 1 or 2 position by C₁ -C₆ -alkoxycarbonyl or a 5- or 6-memberedsaturated or monounsaturated heterocycle which contains one oxygen orsulfur as heteroatom and can be substituted by one to four C₁ -C₄-alkyls.

The present invention also embraces all the stereoisomeric forms of thecompounds Ia and Ib.

The present invention additionally relates to the preparation of thecompounds Ia and Ib, to the use thereof as herbicides, and to mixturesfor controlling undesired plant growth, which contain these compounds Iaand Ib.

The herbicidal action of N-phenyltetrahydroindazoles has been disclosed.Thus, for example, EP-A 105,721 describes derivatives of the formula I'##STR3## where, inter alia, Y is chlorine or bromine,

Z is chlorine or methyl and

R is C₁ -C₄ -alkyl, C₃ -C₄ -alkenyl, C₃ -C₄ -alkynyl, C₁ -C₆-alkoxycarbonylmethyl, C₃ -C₆ -cycloalkoxycarbonylmethyl or C₁ -C₄-halogenoalkoxycarbonylmethyl.

However, there is a search for compounds which, with low applicationrates, have an improved action against undesired plants and aretolerated by crop plants (are selective).

In accordance with this object, we have found theN-phenyltetrahydroindazole derivatives Ia and Ib defined in theintroduction. We have also found processes for the preparation of thesecompounds and the use thereof for the selective control of undesiredplant growth.

The N-phenyltetrahydroindazole derivatives Ia and Ib according to theinvention can be obtained in a variety of ways.

They are obtained, for example, by an appropriately substitutedN-(3-hydroxyphenyl)tetrahydroindazole IIa and IIb being etherified withan appropriate compound IIIa or IIIb in a conventional manner at up to200° C., preferably at from 25° C. to 150° C., in an inert organicsolvent in the presence of a base ##STR4##

IIa (Z=F)

IIb (Z=H)

In the formulae IIIa and IIIb, Nu is a conventional nucleophilic leavinggroup such as halogen, e.g. chlorine, bromine and iodine, orsulfonyloxy, e.g. methylsulfonyloxy, trifluoromethylsulfonyloxy,phenylsulfonyloxy and tolylsulfonyloxy. Nu is preferably chlorine,bromine and tolylsulfonyloxy.

Particularly suitable for the reaction are aprotic polar solvents suchas acetone, acetonitrile, dimethylformamide, dimethyl sulfoxide,tetrahydropyran and corresponding mixtures.

The reaction is preferably carried out in acetone, acetonitrile anddimethylformamide or corresponding mixtures.

Examples of conventionally employed bases are sodium hydroxide,potassium hydroxide, sodium and potassium carbonate, sodium methylateand sodium hydride, the reaction preferably being carried out in thepresence of potassium carbonate or sodium hydride.

The preparation of N-(3-hydroxyphenyl)tetrahydroindazole derivatives IIahas been disclosed (EP-A 105,721). It takes place in 4 stages startingfrom the appropriate nitrophenol derivative IVa as shown below. ##STR5##

The N-(3-hydroxyphenyl)tetrahydroindazole derivatives IIb are obtainedin a similar manner in 6 stages starting from an appropriate nitrophenolderivative IVb, with formation as intermediate of the compounds Ib whereR³ is C₁ -C₄ -alkyl (Alk), as shown below. ##STR6##

It is advisable, for the preparation of compounds Ib in which R³ isunstable under the chlorination conditions (5th stage), to etherify thealcohol IIb with the compound IIIb under conditions similar to thosedescribed for the reaction of IIa with IIIa. Compounds Ib in which R³ isstable to these reaction conditions can be prepared in a manner similarto that shown above.

The individual reaction stages are carried out by conventional methods.

The reaction conditions for the 1st stage (etherification) are, ingeneral and in particular, the same as for the reaction of IIa or IIbwith IIIa or IIIb as described above.

This reaction is preferably carried out in acetone, acetonitrile and/ordimethylformamide in the presence of sodium hydride or potassiumcarbonate as base at from 25° to 150° C.

The reduction of the nitrophenyl ethers Vb to the corresponding anilinederivatives VIb is carried out by conventional methods, for example inthe presence of inorganic reducing agents such as Raney nickel, iron ortin(II) salts, in aprotic or protic polar solvents or in the presence ofhydrogen on noble metal catalysts such as platinum and palladium inaprotic polar solvents.

The isolated aniline derivative IIb is then diazotized with a nitrite inan inert solvent in a conventional manner at from -50° C. to 50° C. andsubsequently reduced in situ. ##STR7##

When an inorganic nitrite, such as nitrous acid and alkali metalnitrites, is used for the diazotization, it is preferably carried out inaqueous phase with the addition of mineral acids at from -10° C. to 5°C., whereas diazotization with the conventional organic nitrites, suchas amyl nitrite, is preferably carried out in an aprotic polar solutionat from -10° C. to 25° C.

Irrespective of the diazotization method, in situ reduction to thecorresponding phenylhydrazine VIIb is possible. For this, an inorganicreducing agent such as a tin(II) salt, an alkali metal sulfite, analkali metal bisulfite and sulfur dioxide is added, as the substance orin solution, to the resulting reaction mixture at from -20° C. to 25° C.

The phenylhydrazine derivative VIIb obtained in this way is subsequentlycyclized with a cyclohexanone derivative VIII in an inert organicsolvent at up to 200° C., preferably at from 25° C. to 150° C., in thepresence or absence of a base. ##STR8##

X in formula VIII is a nucleophilic leaving group. Suitable examples ofthis are halogen such as chlorine and bromine, alkoxy such as methoxy,ethoxy, propyloxy and isopropyloxy, and sulfonates such as tosylate.

Depending on the meaning of X, the reaction is carried out in protic oraprotic polar or aprotic non-polar solvents in the presence or absenceof a base.

Where X is halogen, it is preferably carried out in the presence of abase in an aprotic polar or aprotic non-polar solvent.

Particularly suitable bases for this are tertiary amines such astriethylamine, diisopropylethylamine, N,N-dimethylaniline,N,N-dimethyl-p-aminopyridine, pyridine, isoquinoline,N-methylpyrrolidine, N,N,N',N'-tetramethylethylenediamine,1,5-diazabicyclo[4.3.0]non-5-ene (DBN) and1,8-diazabicyclo[5.4.0]undec-7-ene (DBU).

Examples of suitable solvents are toluene, xylene, chloroform andtetrahydrofuran, and corresponding mixtures.

Toluene or chloroform is preferably used in the presence oftriethylamine, pyridine or DBU as base.

Where X is an alcoholate or sulfonate, protic polar solvents such as, inparticular, glacial acetic acid are preferred. In this case the reactionis carried out without addition of a base.

The indazole derivative IXb obtained in this way is chlorinated to theN-phenyltetrahydroindazole derivative Ib (R³ =alkyl) in a conventionalmanner using a conventional chlorinating reagent. ##STR9##

This reaction takes place at up to 200° C., preferably from 50° to 180°C., in the presence of an inert organic solvent and in the presence orabsence of a base.

Examples of suitable chlorinating agents are oxychlorides such asphosphorus oxytrichloride, thionyl chloride, phosgene or trichloromethylchloroformate, as well as chlorides such as phosphorus trichloride,phosphorus pentachloride or sulfur tetrachloride. Phosphorusoxytrichloride is preferably used.

Examples of suitable solvents are toluene, xylene, chloroform andmethylene chloride, in particular toluene and chloroform.

Suitable bases are the abovementioned tertiary amines.

The reaction with phosphorus oxytrichloride without added solvent andthe reaction with trichloromethyl chloroformate in toluene or chloroformas solvent are particularly preferred.

The derivatives Ib in which R³ is unstable under the conditionsdescribed above can be obtained from these N-phenyltetrahydroindazolederivatives Ib according to the invention, in which R³ is C₁ -C₄ -alkyl(alk), in conventional ways by ether cleavage and subsequentetherification. ##STR10##

For the ether cleavage the N-alkoxyphenyltetrahydroindazole derivativeIb (R³ =alk) is reacted in a conventional manner with a Lewis acid in aninert organic solvent at from 0° C. to 150° C.

Examples of particularly suitable Lewis acids for this are borontrifluoride and its etherate, aluminum trichloride, phosphorustrichloride and boron tribromide.

Preferred solvents are ethers such as tetrahydrofuran, halogenatedhydrocarbons such as chloroform and hydrocarbons such as toluene andcorresponding mixtures.

The subsequent reaction of the N-(3-hydroxyphenyl)tetrahydroindazole IIbwith the nucleophilic reagent IIIb is carried out under conditionssimilar to those described above for the reaction of IIa and IIIa.

With regard to the intended use of the compounds Ia and Ib, thefollowing substituents are suitable:

R¹ is halogen such as fluorine, chlorine and bromine, in particularchlorine;

R² is alkoxycarbonylalkenyl such as 2-methoxycarbonyl-2-propenyl,2-ethoxycarbonyl-2-propenyl, 2-propyloxycarbonyl-2-propenyl,2-(i-propyloxycarbonyl)-2-propenyl, 2-methoxycarbonyl-2-butenyl,2-ethoxycarbonyl-2-butenyl, 2-propyloxycarbonyl-2-butenyl,2-(i-propyloxycarbonyl)-2-butenyl; alkyl such as methyl, ethyl, propyland 1-methylethyl, preferably methyl and ethyl, which is substituted inthe 1 or 2 position by one of the following:

alkoxycarbonyl such as methoxycarbonyl, ethoxycarbonyl,propyloxycarbonyl, 1-methylethoxycarbonyl, butyloxycarbonyl,1-methylpropyloxycarbonyl, 2-methylpropyloxycarbonyl and1,1-dimethylethoxycarbonyl;

or a 5- or 6-membered saturated or singly unsaturated heterocycle whichcontains an oxygen or sulfur, such as tetrahydrofuranyl,tetrahydrothienyl, 2,3-dihydrofuranyl, 2,5-dihydrofuranyl,2,3-dihydrothienyl, 2,5-dihydrothienyl, tetrahydropyranyl,tetrahydrothiopyranyl, 2H-3,4-dihydropyranyl, 2H-5,6-dihydropyranyl,2H-3,4-dihydrothiopyranyl and 2H-5,6-dihydrothiopyranyl, preferablytetrahydrofuranyl, tetrahydrothienyl, tetrahydropyranyl,tetrahydrothiopyranyl, 2H-3,4-dihydropyranyl, 2H-5,6-dihydropyranyl,2H-3,4-dihydrothiopyranyl and 2H-5,6-dihydrothiopyranyl, it beingpossible for these rings to be substituted by up to 4 of the alkylsmentioned under R², preferably by one to four methyls; all possiblesteric arrangements may occur in the case of substituted rings;

R³ is alkyl such as ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl,2-methylpropyl and 1,1-dimethylethyl, pentyl, 1-methylbutyl,2-methylbutyl, 3-methylbutyl, 1,2-dimethylpropyl, 1,1-dimethylpropyl,2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1-methylpentyl,2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,2-dimethylbutyl,1,3-dimethylbutyl, 2,3-dimethylbutyl, 1,1-dimethylbutyl,2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,1,2-trimethylpropyl,1,2,2-trimethylpropyl, 1-ethylbutyl, 2-ethylbutyl and1-ethyl-2-methylpropyl, as well as the isomeric heptyls;

alkenyl such as 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl,2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl,2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl,3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl,3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl,3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl,3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1,1-dimethyl-1-propenyl,1,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl,1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl,1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl,4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl,3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl,2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl,1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl,4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl,1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl,1,3-dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl,2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl,2,3-dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl, 1-ethyl-1-butenyl,1-ethyl-2-butenyl, 1-ethyl-3 -butenyl, 2-ethyl-1-butenyl,2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl,1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl and1-ethyl-2-methyl-2-propenyl;

alkynyl such as 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl,1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl,1-methyl-3-butynyl, 2-methyl-3-butynyl, 1-methyl-2-butynyl,3-methyl-1-butynyl, 1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl,1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl,1-methyl-2-pentynyl, 1-methyl-3-pentynyl, 1-methyl-4-pentynyl,2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3-methyl-1-pentynyl,3-methyl-4-pentynyl, 4-methyl-1-pentynyl, 4-methyl-2-pentynyl,1,1-dimethyl-2-butynyl, 1,1-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl,2,2-dimethyl-3-butynyl, 3,3-dimethyl-1-butynyl, 1-ethyl-2-butynyl,1-ethyl-3-butynyl, 2-ethyl-3-butynyl and 1-ethyl-1-methyl-2-propynyl; oran R² which has, in general and in particular, the abovementionedmeaning.

Specific examples of particularly active compounds Ia and Ib are listedin Tables A, B and C which follow.

                  TABLE A                                                         ______________________________________                                         ##STR11##                     Ia                                             R.sup.1   R'        R"                                                        ______________________________________                                        Cl        H         CO.sub.2 CH.sub.3                                         Cl        CH.sub.3  CO.sub.2 CH.sub.3                                         Br        H         CO.sub.2 CH.sub.3                                         Br        CH.sub.3  CO.sub.2 CH.sub.3                                         Cl        H         CO.sub.2 CH.sub.2 CH.sub.3                                Cl        CH.sub.3  CO.sub.2 CH.sub.2 CH.sub.3                                Br        H         CO.sub.2 CH.sub.2 CH.sub.3                                Br        CH.sub.3  CO.sub.2 CH.sub.2 CH.sub.3                                Cl        H         CO.sub.2 CH(CH.sub.3).sub.2                               Cl        CH.sub.3  CO.sub.2 CH(CH.sub.3).sub.2                               Br        H         CO.sub.2 CH(CH.sub.3).sub.2                               Br        CH.sub.3  CO.sub.2 CH(CH.sub.3).sub.2                               Cl        H         CHCHCO.sub.2 CH.sub.3                                     Cl        CH.sub.3  CHCHCO.sub.2 CH.sub.3                                     Br        H         CHCHCO.sub.2 CH.sub.3                                     Br        CH.sub.3  CHCHCO.sub.2 CH.sub.3                                     Cl        H         CHCHCO.sub.2 CH.sub.2 CH.sub.3                            Cl        CH.sub.3  CHCHCO.sub.2 CH.sub.2 CH.sub.3                            Br        H         CHCHCO.sub.2 CH.sub.2 CH.sub.3                            Br        CH.sub.3  CHCHCO.sub.2 CH.sub.2 CH.sub.3                            Cl        H         CHCHCO.sub.2 CH(CH.sub.3).sub.2                           Cl        CH.sub.3  CHCHCO.sub.2 CH(CH.sub.3).sub.2                           Br        H         CHCHCO.sub.2 CH(CH.sub.3).sub.2                           Br        CH.sub.3  CHCHCO.sub.2 CH(CH.sub.3).sub.2                           Cl        H         CH.sub.2 CO.sub.2 CH.sub.3                                Cl        CH.sub.3  CH.sub.2 CO.sub.2 CH.sub.3                                Br        H         CH.sub.2 CO.sub.2 CH.sub.3                                Br        CH.sub.3  CH.sub.2 CO.sub.2 CH.sub.3                                Cl        H         CH.sub.2 CO.sub.2 CH.sub.2 CH.sub.3                       Cl        CH.sub.3  CH.sub.3 CO.sub.2 CH.sub.2 CH.sub.3                       Br        H         CH.sub.2 CO.sub.2 CH.sub.2 CH.sub.3                       Br        CH.sub.3  CH.sub.2 CO.sub.2 CH.sub.2 CH.sub.3                       Cl        H         CH.sub.2 CO.sub.2 CH(CH.sub.3).sub.2                      Cl        CH.sub.3  CH.sub.2 CO.sub.2 CH(CH.sub.3).sub.2                      Br        H         CH.sub.2 CO.sub.2 CH(CH.sub.3).sub.2                      Br        CH.sub.3  CH.sub.2 CO.sub.2 CH(CH.sub.3).sub.2                      Cl        H         CHC(CH.sub. 3)CO.sub.2 CH.sub.3                           Cl        CH.sub.3  CHC(CH.sub.3)CO.sub.2 CH.sub.3                            Br        H         CHC(CH.sub.3)CO.sub.2 CH.sub.3                            Br        CH.sub.3  CHC(CH.sub.3)CO.sub.2 CH.sub.3                            Cl        H         CHC(CH.sub.3)CO.sub.2 CH.sub.2 CH.sub.3                   Cl        CH.sub.3  CHC(CH.sub.3)CO.sub.2 CH.sub.2 CH.sub.3                   Br        H         CHC(CH.sub.3)CO.sub.2 CH.sub.2 CH.sub.3                   Br        CH.sub.3  CHC(CH.sub.3)CO.sub.2 CH.sub.2 CH.sub.3                   Cl        H         CHC(CH.sub.3)CO.sub.2 CH(CH.sub.3).sub.2                  Cl        CH.sub.3  CHC(CH.sub.3)CO.sub.2 CH(CH.sub.3).sub.2                  Br        H         CHC(CH.sub.3)CO.sub.2 CH(CH.sub.3).sub.2                  Br        CH.sub.3  CHC(CH.sub.3)CO.sub.2 CH(CH.sub.3).sub.2                  Cl        H                                                                                        ##STR12##                                                Cl        CH.sub.3                                                                                 ##STR13##                                                Br        H                                                                                        ##STR14##                                                Br        CH.sub.3                                                                                 ##STR15##                                                Cl        H                                                                                        ##STR16##                                                Cl        CH.sub.3                                                                                 ##STR17##                                                Br        H                                                                                        ##STR18##                                                Br        CH.sub.3                                                                                 ##STR19##                                                Cl        H                                                                                        ##STR20##                                                Cl        CH.sub.3                                                                                 ##STR21##                                                Br        H                                                                                        ##STR22##                                                Br        CH.sub.3                                                                                 ##STR23##                                                Cl        H                                                                                        ##STR24##                                                Cl        CH.sub.3                                                                                 ##STR25##                                                Br        H                                                                                        ##STR26##                                                Br        CH.sub.3                                                                                 ##STR27##                                                Cl        H                                                                                        ##STR28##                                                Cl        CH.sub.3                                                                                 ##STR29##                                                Br        H                                                                                        ##STR30##                                                Br        CH.sub.3                                                                                 ##STR31##                                                Cl        H                                                                                        ##STR32##                                                Cl        CH.sub.3                                                                                 ##STR33##                                                Br        H                                                                                        ##STR34##                                                Br        CH.sub.3                                                                                 ##STR35##                                                Cl        H                                                                                        ##STR36##                                                Cl        CH.sub.3                                                                                 ##STR37##                                                Br        H                                                                                        ##STR38##                                                Br        CH.sub.3                                                                                 ##STR39##                                                Cl        H                                                                                        ##STR40##                                                Cl        CH.sub.3                                                                                 ##STR41##                                                Br        H                                                                                        ##STR42##                                                Br        CH.sub.3                                                                                 ##STR43##                                                Cl        H                                                                                        ##STR44##                                                Cl        CH.sub.3                                                                                 ##STR45##                                                Br        H                                                                                        ##STR46##                                                Br        CH.sub.3                                                                                 ##STR47##                                                Cl        H                                                                                        ##STR48##                                                Cl        CH.sub.3                                                                                 ##STR49##                                                Br        H                                                                                        ##STR50##                                                Br        CH.sub.3                                                                                 ##STR51##                                                Cl        H                                                                                        ##STR52##                                                Cl        CH.sub.3                                                                                 ##STR53##                                                Br        H                                                                                        ##STR54##                                                Br        CH.sub.3                                                                                 ##STR55##                                                Cl        H                                                                                        ##STR56##                                                Cl        CH.sub.3                                                                                 ##STR57##                                                Br        H                                                                                        ##STR58##                                                Br        CH.sub.3                                                                                 ##STR59##                                                Cl        H                                                                                        ##STR60##                                                Cl        CH.sub.3                                                                                 ##STR61##                                                Br        H                                                                                        ##STR62##                                                Br        CH.sub.3                                                                                 ##STR63##                                                Cl        H                                                                                        ##STR64##                                                Cl        CH.sub.3                                                                                 ##STR65##                                                Br        H                                                                                        ##STR66##                                                Br        CH.sub.3                                                                                 ##STR67##                                                Cl        H                                                                                        ##STR68##                                                Cl        CH.sub.3                                                                                 ##STR69##                                                Br        H                                                                                        ##STR70##                                                Br        CH.sub.3                                                                                 ##STR71##                                                Cl        H                                                                                        ##STR72##                                                Cl        CH.sub.3                                                                                 ##STR73##                                                Br        H                                                                                        ##STR74##                                                Br        CH.sub.3                                                                                 ##STR75##                                                Cl        H                                                                                        ##STR76##                                                Cl        CH.sub.3                                                                                 ##STR77##                                                Br        H                                                                                        ##STR78##                                                Br        CH.sub.3                                                                                 ##STR79##                                                Cl        H                                                                                        ##STR80##                                                Cl        CH.sub.3                                                                                 ##STR81##                                                Br        H                                                                                        ##STR82##                                                Br        CH.sub.3                                                                                 ##STR83##                                                Cl        H                                                                                        ##STR84##                                                Cl        CH.sub.3                                                                                 ##STR85##                                                Br        H                                                                                        ##STR86##                                                Br        CH.sub.3                                                                                 ##STR87##                                                Cl        H                                                                                        ##STR88##                                                Cl        CH.sub.3                                                                                 ##STR89##                                                Br        H                                                                                        ##STR90##                                                Br        CH.sub.3                                                                                 ##STR91##                                                Cl        H                                                                                        ##STR92##                                                Cl        CH.sub.3                                                                                 ##STR93##                                                Br        H                                                                                        ##STR94##                                                Br        CH.sub.3                                                                                 ##STR95##                                                Cl        H                                                                                        ##STR96##                                                Cl        CH.sub.3                                                                                 ##STR97##                                                Br        H                                                                                        ##STR98##                                                Br        CH.sub.3                                                                                 ##STR99##                                                Cl        H                                                                                        ##STR100##                                               Cl        CH.sub.3                                                                                 ##STR101##                                               Br        H                                                                                        ##STR102##                                               Br        CH.sub.3                                                                                 ##STR103##                                               Cl        H                                                                                        ##STR104##                                               Cl        CH.sub.3                                                                                 ##STR105##                                               Br        H                                                                                        ##STR106##                                               Br        CH.sub.3                                                                                 ##STR107##                                               F         H         CO.sub.2 CH.sub.3                                         F         CH.sub.3  CO.sub.2 CH.sub.3                                         F         H         CO.sub.2 CH.sub.2 CH.sub.3                                F         CH.sub.3  CO.sub.2 CH.sub.2 CH.sub.3                                F         H         CO.sub.2 CH(CH.sub.3).sub.2                               F         CH.sub.3  CO.sub.2 CH(CH.sub.3).sub.2                               F         H         CHCHCO.sub.2 CH.sub.3                                     F         CH.sub.3  CHCHCO.sub.2 CH.sub.3                                     F         H         CHCHCO.sub.2 CH.sub.2 CH.sub.3                            F         CH.sub.3  CHCHCO.sub.2 CH.sub.2 CH.sub.3                            F         H         CHCHCO.sub.2 CH(CH.sub.3).sub.2                           F         CH.sub.3  CHCHCO.sub.2 CH(CH.sub.3).sub.2                           F         H         CH.sub.2 CO.sub.2 CH.sub.3                                F         CH.sub.3  CH.sub.2 CO.sub.2 CH.sub.3                                F         H         CH.sub.2 CO.sub.2 CH.sub.2 CH.sub.3                       F         CH.sub.3  CH.sub.2 CO.sub.2 CH.sub.2 CH.sub.3                       F         H         CH.sub.2 CO.sub.2 CH(CH.sub.3).sub.2                      F         CH.sub.3  CH.sub.3 CO.sub.2 CH(CH.sub.3).sub.2                      F         H         CHC(CH.sub.3)CO.sub.2 CH.sub.3                            F         CH.sub.3  CHC(CH.sub.3)CO.sub.2 CH.sub.3                            F         H         CHC(CH.sub.3)CO.sub.2 CH.sub.2 CH.sub.3                   F         CH.sub.3  CHC(CH.sub.3)CO.sub.2 CH.sub.2 CH.sub.3                   F         H         CHC(CH.sub.3)CO.sub.2 CH(CH.sub.3).sub.2                  F         CH.sub.3  CHC(CH.sub.3)CO.sub.2 CH(CH.sub.3).sub.2                  F         H                                                                                        ##STR108##                                               F         CH.sub.3                                                                                 ##STR109##                                               F         H                                                                                        ##STR110##                                               F         CH.sub.3                                                                                 ##STR111##                                               F         H                                                                                        ##STR112##                                               F         CH.sub.3                                                                                 ##STR113##                                               F         H                                                                                        ##STR114##                                               F         CH.sub.3                                                                                 ##STR115##                                               F         H                                                                                        ##STR116##                                               F         CH.sub.3                                                                                 ##STR117##                                               F         H                                                                                        ##STR118##                                               F         CH.sub.3                                                                                 ##STR119##                                               F         H                                                                                        ##STR120##                                               F         CH.sub.3                                                                                 ##STR121##                                               F         H                                                                                        ##STR122##                                               F         CH.sub.3                                                                                 ##STR123##                                               F         H                                                                                        ##STR124##                                               F         CH.sub.3                                                                                 ##STR125##                                               F         H                                                                                        ##STR126##                                               F         CH.sub.3                                                                                 ##STR127##                                               F         H                                                                                        ##STR128##                                               F         CH.sub.3                                                                                 ##STR129##                                               F         H                                                                                        ##STR130##                                               F         CH.sub.3                                                                                 ##STR131##                                               F         H                                                                                        ##STR132##                                               F         CH.sub.3                                                                                 ##STR133##                                               F         H                                                                                        ##STR134##                                               F         CH.sub.3                                                                                 ##STR135##                                               F         H                                                                                        ##STR136##                                               F         CH.sub.3                                                                                 ##STR137##                                               F         H                                                                                        ##STR138##                                               F         CH.sub.3                                                                                 ##STR139##                                               F         H                                                                                        ##STR140##                                               F         CH.sub.3                                                                                 ##STR141##                                               F         H                                                                                        ##STR142##                                               F         CH.sub.3                                                                                 ##STR143##                                               F         H                                                                                        ##STR144##                                               F         CH.sub.3                                                                                 ##STR145##                                               F         H                                                                                        ##STR146##                                               F         CH.sub.3                                                                                 ##STR147##                                               F         H                                                                                        ##STR148##                                               F         CH.sub.3                                                                                 ##STR149##                                               F         H                                                                                        ##STR150##                                               F         CH.sub.3                                                                                 ##STR151##                                               F         H                                                                                        ##STR152##                                               F         CH.sub.3                                                                                 ##STR153##                                               F         H                                                                                        ##STR154##                                               F         CH.sub.3                                                                                 ##STR155##                                               F         H                                                                                        ##STR156##                                               F         CH.sub.3                                                                                 ##STR157##                                               ______________________________________                                    

                  TABLE B                                                         ______________________________________                                         ##STR158##                                                                                                  Ib                                                    R.sup.1   R.sup.3                                                      ______________________________________                                               Br        CH.sub.3                                                            Cl        CH.sub.2 CH.sub.3                                                   Br        CH.sub.2 CH.sub.3                                                   Cl        (CH.sub.2).sub.2 CH.sub.3                                           Br        (CH.sub.2).sub.2 CH.sub.3                                           Cl        CH(CH.sub.3).sub.2                                                  Br        CH(CH.sub.3).sub.2                                                  Cl        (CH.sub.2).sub.3 CH.sub.3                                           Br        (CH.sub.2).sub.3 CH.sub.3                                           Cl        CH(CH.sub.3)CH.sub.2 CH.sub.3                                       Br        CH(CH.sub.3)CH.sub.2 CH.sub.3                                       Cl        CH.sub.2 CH(CH.sub.3).sub.2                                         Br        CH.sub.2 CH(CH.sub.3).sub.2                                         Cl        CH.sub.2 CHCH.sub.2                                                 Br        CH.sub.2 CHCH.sub.2                                                 Cl        CH.sub.2 CHCHCH.sub.3                                               Br        CH.sub.2 CHCHCH.sub.3                                               Cl        CH.sub.2 CCH                                                        Br        CH.sub.2 CCH                                                        Cl        CH.sub.2 CCCH.sub.3                                                 Br        CH.sub.2 CCCH.sub.3                                                 F         CH.sub.3                                                            F         CH.sub.2 CH.sub.3                                                   F         (CH.sub.2).sub.2 CH.sub.3                                           F         CH(CH.sub.3).sub.2                                                  F         (CH.sub.2).sub.3 CH.sub.3                                           F         CH(CH.sub.3)CH.sub.2 CH.sub.3                                       F         CH.sub.2 CH(CH.sub.3).sub.2                                         F         CH.sub.2 CHCH.sub.2                                                 F         CH.sub.2 CHCHCH.sub.3                                               F         CH.sub.2 CCH                                                        F         CH.sub.2 CCCH.sub.3                                          ______________________________________                                    

                  TABLE C                                                         ______________________________________                                         ##STR159##                    Ib                                             R.sup.1   R'        R"                                                        ______________________________________                                        Cl        H         CO.sub.2 CH.sub.3                                         Cl        CH.sub.3  CO.sub.2 CH.sub.3                                         Br        H         CO.sub.2 CH.sub.3                                         Br        CH.sub.3  CO.sub.2 CH.sub.3                                         Cl        H         CO.sub.2 CH.sub.2 CH.sub.3                                Cl        CH.sub.3  CO.sub.2 CH.sub.2 CH.sub.3                                Br        H         CO.sub.2 CH.sub.2 CH.sub.3                                Br        CH.sub.3  CO.sub.2 CH.sub.2 CH.sub.3                                Cl        H         CO.sub.2 CH(CH.sub.3).sub.2                               Cl        CH.sub.3  CO.sub.2 CH(CH.sub.3).sub.2                               Br        H         CO.sub.2 CH(CH.sub.3).sub.2                               Br        CH.sub.3  CO.sub.2 CH(CH.sub.3).sub.2                               Cl        H         CHCHCO.sub.2 CH.sub.3                                     Cl        CH.sub.3  CHCHCO.sub.2 CH.sub.3                                     Br        H         CHCHCO.sub.2 CH.sub.3                                     Br        CH.sub.3  CHCHCO.sub.2 CH.sub.3                                     Cl        H         CHCHCO.sub.2 CH.sub.2 CH.sub.3                            Cl        CH.sub.3  CHCHCO.sub.2 CH.sub.2 CH.sub.3                            Br        H         CHCHCO.sub.2 CH.sub.2 CH.sub.3                            Br        CH.sub.3  CHCHCO.sub.2 CH.sub.2 CH.sub.3                            Cl        H         CHCHCO.sub.2 CH(CH.sub.3).sub.2                           Cl        CH.sub.3  CHCHCO.sub.2 CH(CH.sub.3).sub.2                           Br        H         CHCHCO.sub.2 CH(CH.sub.3).sub.2                           Br        CH.sub.3  CHCHCO.sub.2 CH(CH.sub.3).sub.2                           Cl        H         CH.sub.2 CO.sub.2 CH.sub.3                                Cl        CH.sub.3  CH.sub.2 CO.sub.2 CH.sub.3                                Br        H         CH.sub.2 CO.sub.2 CH.sub.3                                Br        CH.sub.3  CH.sub.2 CO.sub.2 CH.sub.3                                Cl        H         CH.sub.2 CO.sub.2 CH.sub.2 CH.sub.3                       Cl        CH.sub.3  CH.sub.2 CO.sub.2 CH.sub.2 CH.sub.3                       Br        H         CH.sub.2 CO.sub.2 CH.sub.2 CH.sub.3                       Br        CH.sub.3  CH.sub.2 CO.sub.2 CH.sub.2 CH.sub.3                       Cl        H         CH.sub.2 CO.sub.2 CH(CH.sub.3).sub.2                      Cl        CH.sub.3  CH.sub.2 CO.sub.2 CH(CH.sub.3).sub.2                      Br        H         CH.sub.2 CO.sub.2 CH(CH.sub.3).sub.2                      Br        CH.sub.3  CH.sub.2 CO.sub.2 CH(CH.sub.3).sub.2                      Cl        H         CHC(CH.sub.3)CO.sub.2 CH.sub. 3                           Cl        CH.sub.3  CHC(CH.sub.3)CO.sub.2 CH.sub.3                            Br        H         CHC(CH.sub.3)CO.sub.2 CH.sub.3                            Br        CH.sub.3  CHC(CH.sub.3)CO.sub.2 CH.sub.3                            Cl        H         CHC(CH.sub.3)CO.sub.2 CH.sub.2 CH.sub.3                   Cl        CH.sub.3  CHC(CH.sub.3)CO.sub.2 CH.sub.2 CH.sub.3                   Br        H         CHC(CH.sub.3)CO.sub.2 CH.sub.2 CH.sub.3                   Br        CH.sub.3  CHC(CH.sub.3)CO.sub.2 CH.sub.2 CH.sub.3                   Cl        H         CHC(CH.sub.3)CO.sub.2 CH(CH.sub.3).sub.2                  Cl        CH.sub.3  CHC(CH.sub.3)CO.sub.2 CH(CH.sub.3).sub.2                  Br        H         CHC(CH.sub.3)CO.sub.2 CH(CH.sub.3).sub.2                  Br        CH.sub.3  CHC(CH.sub.3)CO.sub.2 CH(CH.sub.3).sub.2                  Cl        H                                                                                        ##STR160##                                               Cl        CH.sub.3                                                                                 ##STR161##                                               Br        H                                                                                        ##STR162##                                               Br        CH.sub.3                                                                                 ##STR163##                                               Cl        H                                                                                        ##STR164##                                               Cl        CH.sub.3                                                                                 ##STR165##                                               Br        H                                                                                        ##STR166##                                               Br        CH.sub.3                                                                                 ##STR167##                                               Cl        H                                                                                        ##STR168##                                               Cl        CH.sub.3                                                                                 ##STR169##                                               Br        H                                                                                        ##STR170##                                               Br        CH.sub.3                                                                                 ##STR171##                                               Cl        H                                                                                        ##STR172##                                               Cl        CH.sub.3                                                                                 ##STR173##                                               Br        H                                                                                        ##STR174##                                               Br        CH.sub.3                                                                                 ##STR175##                                               Cl        H                                                                                        ##STR176##                                               Cl        CH.sub.3                                                                                 ##STR177##                                               Br        H                                                                                        ##STR178##                                               Br        CH.sub.3                                                                                 ##STR179##                                               Cl        H                                                                                        ##STR180##                                               Cl        CH.sub.3                                                                                 ##STR181##                                               Br        H                                                                                        ##STR182##                                               Br        CH.sub.3                                                                                 ##STR183##                                               Cl        H                                                                                        ##STR184##                                               Cl        CH.sub.3                                                                                 ##STR185##                                               Br        H                                                                                        ##STR186##                                               Br        CH.sub.3                                                                                 ##STR187##                                               Cl        H                                                                                        ##STR188##                                               Cl        CH.sub.3                                                                                 ##STR189##                                               Br        H                                                                                        ##STR190##                                               Br        CH.sub.3                                                                                 ##STR191##                                               Cl        H                                                                                        ##STR192##                                               Cl        CH.sub.3                                                                                 ##STR193##                                               Br        H                                                                                        ##STR194##                                               Br        CH.sub.3                                                                                 ##STR195##                                               Cl        H                                                                                        ##STR196##                                               Cl        CH.sub.3                                                                                 ##STR197##                                               Br        H                                                                                        ##STR198##                                               Br        CH.sub.3                                                                                 ##STR199##                                               Cl        H                                                                                        ##STR200##                                               Cl        CH.sub.3                                                                                 ##STR201##                                               Br        H                                                                                        ##STR202##                                               Br        CH.sub.3                                                                                 ##STR203##                                               Cl        H                                                                                        ##STR204##                                               Cl        CH.sub.3                                                                                 ##STR205##                                               Br        H                                                                                        ##STR206##                                               Br        CH.sub.3                                                                                 ##STR207##                                               Cl        H                                                                                        ##STR208##                                               Cl        CH.sub.3                                                                                 ##STR209##                                               Br        H                                                                                        ##STR210##                                               Br        CH.sub.3                                                                                 ##STR211##                                               Cl        H                                                                                        ##STR212##                                               Cl        CH.sub.3                                                                                 ##STR213##                                               Br        H                                                                                        ##STR214##                                               Br        CH.sub.3                                                                                 ##STR215##                                               Cl        H                                                                                        ##STR216##                                               Cl        CH.sub.3                                                                                 ##STR217##                                               Br        H                                                                                        ##STR218##                                               Br        CH.sub.3                                                                                 ##STR219##                                               Cl        H                                                                                        ##STR220##                                               Cl        CH.sub.3                                                                                 ##STR221##                                               Br        H                                                                                        ##STR222##                                               Br        CH.sub.3                                                                                 ##STR223##                                               Cl        H                                                                                        ##STR224##                                               Cl        CH.sub.3                                                                                 ##STR225##                                               Br        H                                                                                        ##STR226##                                               Br        CH.sub.3                                                                                 ##STR227##                                               Cl        H                                                                                        ##STR228##                                               Cl        CH.sub.3                                                                                 ##STR229##                                               Br        H                                                                                        ##STR230##                                               Br        CH.sub.3                                                                                 ##STR231##                                               Cl        H                                                                                        ##STR232##                                               Cl        CH.sub.3                                                                                 ##STR233##                                               Br        H                                                                                        ##STR234##                                               Br        CH.sub.3                                                                                 ##STR235##                                               Cl        H                                                                                        ##STR236##                                               Cl        CH.sub.3                                                                                 ##STR237##                                               Br        H                                                                                        ##STR238##                                               Br        CH.sub.3                                                                                 ##STR239##                                               Cl        H                                                                                        ##STR240##                                               Cl        CH.sub.3                                                                                 ##STR241##                                               Br        H                                                                                        ##STR242##                                               Br        CH.sub.3                                                                                 ##STR243##                                               Cl        H                                                                                        ##STR244##                                               Cl        CH.sub.3                                                                                 ##STR245##                                               Br        H                                                                                        ##STR246##                                               Br        CH.sub.3                                                                                 ##STR247##                                               Cl        H                                                                                        ##STR248##                                               Cl        CH.sub.3                                                                                 ##STR249##                                               Br        H                                                                                        ##STR250##                                               Br        CH.sub.3                                                                                 ##STR251##                                               F         H         CO.sub.2 CH.sub.3                                         F         CH.sub.3  CO.sub.2 CH.sub.3                                         F         H         CO.sub.2 CH.sub.2 CH.sub.3                                F         CH.sub.3  CO.sub.2 CH.sub.2 CH.sub.3                                F         H         CO.sub.2 CH(CH.sub.3).sub.2                               F         CH.sub.3  CO.sub.2 CH(CH.sub.3).sub.2                               F         H         CHCHCO.sub.2 CH.sub.3                                     F         CH.sub.3  CHCHCO.sub.2 CH.sub.3                                     F         H         CHCHCO.sub.2 CH.sub.2 CH.sub.3                            F         CH.sub.3  CHCHCO.sub.2 CH.sub.2 CH.sub.3                            F         H         CHCHCO.sub.2 CH(CH.sub.3).sub.2                           F         CH.sub.3  CHCHCO.sub.2 CH(CH.sub.3).sub.2                           F         H         CH.sub.2 CO.sub.2 CH.sub.3                                F         CH.sub.3  CH.sub.2 CO.sub.2 CH.sub.3                                F         H         CH.sub.2 CO.sub.2 CH.sub.2 CH.sub.3                       F         CH.sub.3  CH.sub.2 CO.sub.2 CH.sub.2 CH.sub.3                       F         H         CH.sub.2 CO.sub.2 CH(CH.sub.3).sub.2                      F         CH.sub.3  CH.sub.2 CO.sub.2 CH(CH.sub.3).sub.2                      F         H         CHC(CH.sub.3)CO.sub.2 CH.sub.3                            F         CH.sub.3  CHC(CH.sub.3)CO.sub.2 CH.sub.3                            F         H         CHC(CH.sub. 3)CO.sub.2 CH.sub.2 CH.sub.3                  F         CH.sub.3  CHC(CH.sub.3)CO.sub.2 CH.sub.2 CH.sub.3                   F         H         CHC(CH.sub.3)CO.sub.2 CH(CH.sub.3).sub.2                  F         CH.sub.3  CHC(CH.sub.3)CO.sub.2 CH(CH.sub.3).sub.2                  F         H                                                                                        ##STR252##                                               F         CH.sub.3                                                                                 ##STR253##                                               F         H                                                                                        ##STR254##                                               F         CH.sub.3                                                                                 ##STR255##                                               F         H                                                                                        ##STR256##                                               F         CH.sub.3                                                                                 ##STR257##                                               F         H                                                                                        ##STR258##                                               F         CH.sub.3                                                                                 ##STR259##                                               F         H                                                                                        ##STR260##                                               F         CH.sub.3                                                                                 ##STR261##                                               F         H                                                                                        ##STR262##                                               F         CH.sub.3                                                                                 ##STR263##                                               F         H                                                                                        ##STR264##                                               F         CH.sub.3                                                                                 ##STR265##                                               F         H                                                                                        ##STR266##                                               F         CH.sub.3                                                                                 ##STR267##                                               F         H                                                                                        ##STR268##                                               F         CH.sub.3                                                                                 ##STR269##                                               F         H                                                                                        ##STR270##                                               F         CH.sub.3                                                                                 ##STR271##                                               F         H                                                                                        ##STR272##                                               F         CH.sub.3                                                                                 ##STR273##                                               F         H                                                                                        ##STR274##                                               F         CH.sub.3                                                                                 ##STR275##                                               F         H                                                                                        ##STR276##                                               F         CH.sub.3                                                                                 ##STR277##                                               F         H                                                                                        ##STR278##                                               F         CH.sub.3                                                                                 ##STR279##                                               F         H                                                                                        ##STR280##                                               F         CH.sub.3                                                                                 ##STR281##                                               F         H                                                                                        ##STR282##                                               F         CH.sub.3                                                                                 ##STR283##                                               F         H                                                                                        ##STR284##                                               F         CH.sub.3                                                                                 ##STR285##                                               F         H                                                                                        ##STR286##                                               F         CH.sub.3                                                                                 ##STR287##                                               F         H                                                                                        ##STR288##                                               F         CH.sub.3                                                                                 ##STR289##                                               F         H                                                                                        ##STR290##                                               F         CH.sub.3                                                                                 ##STR291##                                               F         H                                                                                        ##STR292##                                               F         CH.sub.3                                                                                 ##STR293##                                               F         H                                                                                        ##STR294##                                               F         CH.sub.3                                                                                 ##STR295##                                               F         H                                                                                        ##STR296##                                               F         CH.sub.3                                                                                 ##STR297##                                               ______________________________________                                    

The N-phenyltetrahydroindazole derivatives Ia and Ib, and herbicidalagents containing them, may be applied for instance in the form ofdirectly sprayable solutions, powders, suspensions (includinghigh-percentage aqueous, oily or other suspensions), dispersions,emulsions, oil dispersions, pastes, dusts, broadcasting agents, orgranules by spraying, atomizing, dusting, broadcasting or watering. Theforms of application depend entirely on the purpose for which the agentsare being used, but they must ensure as fine a distribution of theactive ingredients according to the invention as possible.

For the preparation of solutions, emulsions, pastes and oil dispersionsto be sprayed direct, mineral oil fractions of medium to high boilingpoint, such as kerosene or diesel oil, further coal-tar oils, and oilsof vegetable or animal origin, aliphatic, cyclic and aromatichydrocarbons such as toluene, xylene, paraffin, tetrahydronaphthalene,alkylated naphthalenes and their derivatives such as methanol, ethanol,propanol, butanol, cyclohexanol, cyclohexanone, chlorobenzene,isophorone, etc., and strongly polar solvents such asN,N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, water,etc. are suitable.

Aqueous formulations may be prepared from emulsion concentrates, pastes,oil dispersions or wettable powders by adding water. To prepareemulsions, pastes and oil dispersions the ingredients as such ordissolved in an oil or solvent may be homogenized in water by means ofwetting or dispersing agents, adherents or emulsifiers. Concentrateswhich are suitable for dilution with water may be prepared from activeingredient, wetting agent, adherent, emulsifying or dispersing agent andpossibly solvent or oil.

Examples of surfactants are: alkali metal, alkaline earth metal andammonium salts of aromatic sulfonic acids, e.g., ligninsulfonic acid,phenolsulfonic acid, naphthalenesulfonic acid anddibutylnaphthalenesulfonic acid, and of fatty acids, alkyl and alkylarylsulfonates, and alkyl, lauryl ether and fatty alcohol sulfates, alkalimetal and alkaline earth metal salts of dibutylnaphthalenesulfonic acid,lauryl ether sulfate, fatty alcohol sulfates, and salts of sulfatedhexadecanols, heptadecanols, and octadecanols, salts of fatty alcoholglycol ethers, condensation products of sulfonated naphthalene andnaphthalene derivatives with formaldehyde, condensation products ofnaphthalene or naphthalenesulfonic acids with phenol and formaldehyde,polyoxyethylene octylphenol ethers, ethoxylated isooctylphenol,ethoxylated octylphenol and ethoxylated nonylphenol, alkylphenolpolyglycol ethers, tributylphenyl polyglycol ethers, alkylaryl polyetheralcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates,ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylatedpolyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitolesters, lignin-sulfite waste liquors and methyl cellulose.

Powders, dusts and broadcasting agents may be prepared by mixing orgrinding the active ingredients with a solid carrier.

Granules, e.g., coated, impregnated or homogeneous granules, may beprepared by bonding the active ingredients to solid carriers. Examplesof solid carriers are mineral earths such as silicic acid, silica gels,silicates, talc, kaolin, attapulgus clay, limestone, lime, chalk, bole,loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesiumsulfate, magnesium oxide, ground plastics, fertilizers such as ammoniumsulfate, ammonium phosphate, ammonium nitrate, and ureas, and vegetableproducts such as grain meals, bark meal, wood meal, and nutshell meal,cellulosic powders, etc.

The formulations contain from 0.1 to 95, and preferably 0.5 to 90, % byweight of active ingredient.

Examples of formulations are as follows:

I. 90 parts by weight of compound no. 1.001 is mixed with 10 parts byweight of N-methyl-alpha-pyrrolidone. A mixture is obtained which issuitable for application in the form of very fine drops.

II. 20 parts by weight of compound no. 1.004 is dissolved in a mixtureconsisting of 80 parts by weight of xylene, 10 parts by weight of theadduct of 8 to 10 moles of ethylene oxide and 1 mole of oleicacid-N-monoethanolamide, 5 parts by weight of the calcium salt ofdodecylbenzenesulfonic acid, and 5 parts by weight of the adduct of 40moles of ethylene oxide and 1 mole of castor oil. By pouring thesolution into 100,000 parts by weight of water and uniformlydistributing it therein, an aqueous dispersion is obtained containing0.02% by weight of the active ingredient.

III. 20 parts by weight of compound no. 1.006 is dissolved in a mixtureconsisting of 40 parts by weight of cyclohexanone, 30 parts by weight ofisobutanol, 20 parts by weight of the adduct of 7 moles of ethyleneoxide and 1 mole of isooctylphenol, and 10 parts by weight of the adductof 40 moles of ethylene oxide and 1 mole of castor oil. By pouring thesolution into 100,000 parts by weight of water and finely distributingit therein, an aqueous dispersion is obtained containing 0.02% by weightof the active ingredient.

IV. 20 parts by weight of compound no. 1.001 is dissolved in a mixtureconsisting of 25 parts by weight of cyclohexanone, 65 parts by weight ofa mineral oil fraction having a boiling point between 210° and 280° C.,and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1mole of castor oil. By pouring the solution into 100,000 parts by weightof water and uniformly distributing it therein, an aqueous dispersion isobtained containing 0.02% by weight of the active ingredient.

V. 20 parts by weight of compound no. 1.002 is well mixed with 3 partsby weight of the sodium salt of diisobutylnaphthalene-alpha-sulfonicacid, 17 parts by weight of the sodium salt of a lignin-sulfonic acidobtained from a sulfite waste liquor, and 60 parts by weight of powderedsilica gel, and triturated in a hammer mill. By uniformly distributingthe mixture in 20,000 parts by weight of water, a spray liquor isobtained containing 0.1% by weight of the active ingredient.

VI. 3 parts by weight of compound no. 1.005 is intimately mixed with 97parts by weight of particulate kaolin. A dust is obtained containing 3%by weight of the active ingredient.

VII. 30 parts by weight of compound no. 1.003 is intimately mixed with amixture consisting of 92 parts by weight of powdered silica gel and 8parts by weight of paraffin oil which has been sprayed onto the surfaceof this silica gel. A formulation of the active ingredient is obtainedhaving good adherence.

VIII. 20 parts by weight of compound no. 1.004 is intimately mixed with2 parts of the calcium salt of dodecylbenzenesulfonic acid, 8 parts of afatty alcohol polyglycol ether, 2 parts of the sodium salt of aphenolsulfonic acid-urea-formaldehyde condensate and 68 parts of aparaffinic mineral oil. A stable oily dispersion is obtained.

The active ingredients or the herbicidal agents containing them may beapplied pre- or postemergence. If certain crop plants tolerate theactive ingredients less well, application techniques may be used inwhich the herbicidal agents are sprayed from suitable equipment in sucha manner that the leaves of sensitive crop plants are if possible nottouched, and the agents reach the soil or the unwanted plants growingbeneath the crop plants (post-directed, lay-by treatment).

The application rates depend on the objective to be achieved, the timeof the year, the plants to be combated and their growth stage, and arefrom 0.001 to 3.0, preferably 0.01 to 0.5, kg of active ingredient perhectare.

In view of the number of application methods possible, the compoundsaccording to the invention, or agents containing them, may be used in afurther larger number of crops for removing unwanted plants. Thefollowing crops may be mentioned by way of example:

    ______________________________________                                        Botanical name         Common name                                            ______________________________________                                        Allium cepa            onions                                                 Ananas comosus         pineapples                                             Arachis hypogaea       peanuts                                                                       (groundnuts)                                           Asparagus officinalis  asparagus                                              Avena sativa           oats                                                   Beta vulgaris spp. altissima                                                                         sugarbeets                                             Beta vulgaris spp. rapa                                                                              fodder beets                                           Beta vulgaris spp. esculenta                                                                         table beets,                                                                  red beets                                              Brassica napus var. napus                                                                            rapeseed                                               Brassica napus var. napobrassica                                                                     swedes                                                 Brassica napus var. rapa                                                                             turnips                                                Brassica rapa var. silvestris                                                 Camellia sinensis      tea plants                                             Carthamus tinctorius   safflower                                              Carya illinoinensis    pecan trees                                            Citrus limon           lemons                                                 Citrus maxima          grapefruits                                            Citrus reticulata      mandarins                                              Citrus sinensis        orange trees                                           Coffea arabica (Coffea canephora,                                                                    coffee plants                                          Coffea liberica)                                                              Cucumis melo           melons                                                 Cucumis sativus        cucumbers                                              Cynodon dactylon       Bermudagrass                                           Daucus carota          carrots                                                Elais guineensis       oil palms                                              Fragaria vesca         strawberries                                           Glycine max            soybeans                                               Gossypium hirsutum (Gossypium arboreum,                                                              cotton                                                 Gossypium herbaceum, Gossypium vitifolium)                                    Helianthus annuus      sunflowers                                             Helianthus tuberosus   Jerusalem artichoke                                    Hevea brasiliensis     rubber plants                                          Hordeum vulgare        barley                                                 Humulus lupulus        hops                                                   Ipomoea batatas        sweet potatoes                                         Juglans regia          walnut trees                                           Lactuca sativa         lettuce                                                Lens culinaris         lentils                                                Linum usitatissimum    flax                                                   Lycopersicon lycopersicum                                                                            tomatoes                                               Malus spp.             apple trees                                            Manihot esculenta      cassava                                                Medicago sativa        alfalfa (lucerne)                                      Mentha piperita        peppermint                                             Musa spp.              banana plants                                          Nicotiana tabacum (N. rustica)                                                                       tobacco                                                Olea europaea          olive trees                                            Oryza sativa           rice                                                   Panicum miliaceum      millet                                                 Phaseolus lunatus      limabeans                                              Phaseolus mungo        mungbeans                                              Phaseolus vulgaris     snapbeans, green                                                              beans, dry beans                                       Pennisetum glaucum     pearl millet                                           Petroselinum crispum spp. tuberosum                                                                  parsley                                                Picea abies            Norway spruce                                          Abies alba             fir trees                                              Pinus spp.             pine trees                                             Pisum sativum          English peas                                           Prunus avium           cherry trees                                           Prunus domestica       plum trees                                             Prunus dulcis          almond trees                                           Prunus persica         peach trees                                            Pyrus communis         pear trees                                             Ribes sylvestre        redcurrants                                            Ribes uva-crispa       gooseberries                                           Ricinus communis       castor-oil plants                                      Saccharum officinarum  sugar cane                                             Secale cereale         rye                                                    Sesamum indicum        sesame                                                 Solanum tuberosum      Irish potatoes                                         Sorghum bicolor (s. vulgare)                                                                         sorghum                                                Sorghum dochna         sorgo                                                  Spinacia oleracea      spinach                                                Theobroma cacao        cacao plants                                           Trifolium pratense     red clover                                             Triticum aestivum      wheat                                                  Triticum durum         durum wheat                                            Vaccinium corymbosum   blueberries                                            Vaccinium vitis-idaea  cranberries                                            Vicia faba             tick beans                                             Vigna sinensis (V. unguiculata)                                                                      cow peas                                               Vitis vinfera          grapes                                                 Zea mays               Indian corn, sweet                                                            corn, maize                                            ______________________________________                                    

To increase the spectrum of action and to achieve synergistic effects,the N-phenyltetrahydroindazoles of the formula Ia and Ib may be mixedand applied together with numerous representatives of other herbicidalor growth-regulating active ingredient groups. Examples of suitablecomponents are diazines, 4H-3,1-benzoxazine derivatives,benzothiadiazinones, 2,6-dinitroanilines, N-phenylcarbamates,thiolcarbamates, halocarboxylic acids, triazines, amides, ureas,diphenyl ethers, triazinones, uracils, benzofuran derivatives,quinolinecarboxylic acids, phenyloxy- and hetero-aryloxypropionic acidsand salts, esters and amides thereof, etc.

It may also be useful to apply the N-phenyltetrahydroindazoles of theformula Ia and Ib, either alone or in combination with other herbicides,in admixture with other crop protection agents, e.g., agents forcombating pests or phytopathogenic fungi or bacteria. The compounds mayalso be mixed with solutions of mineral salts used to remedy nutritionalor trace element deficiencies. Non-phytotoxic oils and oil concentratesmay also be added.

Synthesis Examples

The directions given in the synthesis examples below may be used, afterappropriate modifications of the starting materials, to obtain furthercompounds of the formula Ia and Ib. The compounds obtained are listedwith their physical data in the tables below; compounds without thesedata may be prepared from the appropriate materials in analogous manner.In view of their close structural relationship to the compounds whichhave been manufactured and investigated, they are expected to have asimilar action.

EXAMPLE 1

Preparation of3-chloro-2-[4-chloro-2-fluoro-5-(5,6-dihydro-2H-pyran-3-ylmethoxy)phenyl]-4,5,6,7-tetrahydroindazole##STR298##

2.1 g (16 mmol) of 3-chloromethyl-5,6-dihydro-2H-pyran were added at 25°C. to a mixture of 4.5 g (15 mmol) of3-chloro-2-(4-chloro-2-fluoro-5-hydroxyphenyl)-4,5,6,7-tetrahydroindazole,2.5 g (18 mmol) of potassium carbonate and 0.5 g (3 mmol) of sodiumiodide in 50 ml of dimethylformamide, and the reaction mixture wasstirred for 12 hours. 100 ml of water were added, and the precipitatewas isolated, washed with water and dried, resulting in 5 g (84%) of thetitle compound [melting point 90° to 92° C.]. Compound No. 1.002.

EXAMPLE 2

Preparation of3-chloro-2-[4-chloro-2-fluoro-5-(3-hexahydrothiopyranylmethoxy)phenyl]-4,5,6,7-tetrahydroindazole##STR299##

a) 47.9 g (250 mmol) of 2-chloro-4-fluoro-5-nitrophenol, 34.6 g (250mmol) of potassium carbonate, 1 g of potassium iodide and 58.5 g (300mmol) of 3-bromomethyltetrahydrothiopyran in 500 ml of acetonitrile wererefluxed for 5 hours. The mixture was cooled to 25° C. and filtered, thesolvent was removed from the filtrate, the residue was taken up inmethylene chloride, and the solution was washed with water, dried andconcentrated. 22 g (29%) of2-chloro-4-fluoro-5-nitro-1-(3-tetrahydrothiopyranylmethoxy)benzene(melting point 100° to 103° C.) were obtained.

b) A suspension of 26 g (85 mmol) of the above nitro compound was addedto a mixture of 14.3 g (260 mmol) of iron powder in 100 ml of methanoland 28 ml of glacial acetic acid at the boiling point, and the mixturewas refluxed for a further 2 hours. The reaction mixture was cooled to25° C. and then poured into water, the mixture was extracted with ethylacetate, and the extracts were dried and concentrated. Purificationresulted in 15.5 g (66%) of4-chloro-2-fluoro-5-(3-tetrahydrothiopyranylmethoxy)aniline (meltingpoint 66° to 68° C.).

c) 100 ml of 10% strength hydrochloric acid were added to a solution of13.8 g (50 mmol) of4-chloro-2-fluoro-5-(3-tetrahydrothiopyranylmethoxy)aniline in 50 ml ofglacial acetic acid and then, at -5° to 0° C., 3.5 g (50 mmol) of sodiumnitrite in 20 ml of water were added within 15 min.

The solution obtained after stirring at this temperature for 1 hour wasadded dropwise, at -10° to -5° C., to 28.2 g (125 mmol) of tin(II)chloride dihydrate in 30 ml of concentrated hydrochloric acid, and themixture was stirred at 0° C. for a further 2 hours. While cooling inice, the mixture was made alkaline with concentrated sodium hydroxidesolution and was extracted with methylene chloride, the organic phaseswere dried and concentrated, and the residue was stirred with petroleumether. 12 g (82%) of4-chloro-2-fluoro-5-(3-tetrahydrothiopyranylmethoxy)phenylhydrazine(melting point 83° to 87° C.) were obtained.

d) 7.3 g (25 mmol) of the phenylhydrazine obtained in this way wereadded to 4.3 g (25 mmol) of ethyl cyclohexanone-2-carboxylate in 100 mlof glacial acetic acid, and the mixture was refluxed for 5 hours. It wascooled to 25° C. and then concentrated, precipitation was carried out byadding a little water/petroleum ether, and the residue was dried. 9 g(90%) of2-[4-chloro-2-fluoro-5-(3-tetrahydrothiopyranylmethoxy)phenyl]-1,2,4,5,6,7-hexahydro-3H-indazol-3-one(melting point 96° to 100° C.) were obtained.

e) 8.7 g (22 mmol) of the above 3-indazolone were added to a solution of30 ml of trichloromethyl chloroformate in 500 ml of toluene and themixture was slowly heated. After cooling to 25° C. it was flushed withnitrogen, concentrated and purified as usual. 2 g (22%) of the titlecompound were obtained as an oil (compound No. 1.005).

Use examples

The action of the N-phenyltetrahydroindazole derivatives Ia and Ib onthe growth of test plants is demonstrated in the following greenhouseexperiments.

The vessels employed were plastic flowerpots having a volume of 300 cm³and filled with a sandy loam containing about 3.0% humus. The seeds ofthe test plants were sown separately, according to species.

For the postemergence treatment, either plants sown directly in the potsand grown there were used, or plants which were cultivated separately asseedlings and were transplanted to the vessels a few days beforetreatment.

Depending on growth form, the plants were grown to a height of 3 to 15cm before being treated with the active ingredients, which weresuspended or emulsified in water and sprayed through finely distributingnozzles. The application rate for postemergence treatment was 0.03kg/ha.

The pots were set up in the greenhouse, species from warmer climates inwarmer areas (20° to 35° C.) and species from moderate climates at 10°to 20° C. The experiments were run for from 2 to 4 weeks. During thistime the plants were tended and their reactions to the varioustreatments assessed.

The assessment scale was 0 to 100, 100 denoting nonemergence or completedestruction of at least the visible plant parts, and 0 denoting nodamage or normal growth.

The plants used in the greenhouse experiments were Abutilon theophrasti,Amaranthus retroflexus, Chenopodium album, Chrysanthemum corinarium,Galium aparine, Ipomoea spp., Lamium amplexicaule, Malva neglecta,Solanum nigrum and Stellaria media.

Compounds 1.005, 1.003, 1.001 and 1.002, applied postemergence at a rateof 0.03 kg/ha, provide excellent control of unwanted broadleaved plants.

                                      TABLE 1                                     __________________________________________________________________________     ##STR300##                                Ia                                                           Physical data:                                      Compound No.                                                                          R.sup.1                                                                         R'                                                                              R"            [mp (°C.); IR(cm.sup.-1); .sup.1 H-NMR                                 (ppm)]                                              __________________________________________________________________________    1.001   Cl                                                                              H                                                                                ##STR301##   NMR: 7.0(d), 7.35(d)                                1.002   Cl                                                                              H                                                                                ##STR302##   mp: 90-92                                           1.003   Cl                                                                              H                                                                                ##STR303##   IR: 2935, 1505, 1448, 1393, 1197                    1.004   Cl                                                                              H                                                                                ##STR304##   mp: 113-115                                         1.005   Cl                                                                              H                                                                                ##STR305##   IR: 2926, 1504, 1466, 1393, 1197                    1.006   Cl                                                                              H CHC(CH.sub.3)CO.sub.2 CH.sub.2 CH.sub. 3                                                    mp: 93-95                                           1.007   Cl                                                                              H                                                                                ##STR306##   IR: 2935, 1505, 1393, 1197                          1.008   Cl                                                                              H                                                                                ##STR307##   mp: 70-71                                           1.009   Cl                                                                              H                                                                                ##STR308##   IR: 2936. 1504, 1198. 1049                          __________________________________________________________________________

                                      TABLE 2                                     __________________________________________________________________________     ##STR309##                                                                                                               Ib                                                           Physical data:                                     Compound No.                                                                          R.sup.1                                                                          R.sup.3         [mp (°C.); IR (cm.sup.-1); .sup.1 H-NMR                                (ppm)]                                             __________________________________________________________________________    2.001   Cl CH.sub.2 CHC(CH.sub.3)CO.sub.2 CH.sub.3                                                       mp: 82-85                                          2.002   Cl CH.sub.2 CHC(CH.sub.3)CO.sub.2 CH.sub.2 CH.sub.3                                              mp: 75-76                                          2.003   Cl CH.sub.2 CH.sub.3                                                                             mp: 63-65                                          2.004   Cl CH.sub.2 CHCH.sub.2                                                                           mp: 74-76                                          2.005   Cl CH.sub.2 CCH    mp: 99-100                                         2.006   Cl CH(CH.sub.3).sub.2                                                                            IR: 2936, 1594, 1492, 1060                         2.007   Cl CH(CH.sub.3)CCH mp: 65-67                                          2.008   Cl (CH.sub.2).sub.4 CH(CH.sub.3).sub.2                                                           IR: 2936, 1595, 1494, 1063                         2.009   Cl CH.sub.2 C(CH.sub.3).sub.3                                                                    IR: 2954, 2936, 1594, 1494, 1400, 1064             2.010   Cl (CH.sub.2).sub.5 CH.sub.3                                                                     mp: 45-47                                          __________________________________________________________________________

                  TABLE 3                                                         ______________________________________                                         ##STR310##                    Ib                                             Com-                          Physical data:                                  pound                         [mp (°C.); IR (cm.sup.-1);               No.   R.sup.1                                                                             R'    R"          .sup.1 H-NMR (ppm)]                             ______________________________________                                        3.001 Cl    H                                                                                    ##STR311## mp: 62-65                                       3.002 Cl    H                                                                                    ##STR312## mp: 63-65                                       3.003 Cl    H                                                                                    ##STR313## IR: 2935, 1593, 1494, 1094, 1063                3.004 Cl    H                                                                                    ##STR314## IR: 2935, 1593, 1493, 1061                      3.005 Cl    H                                                                                    ##STR315## mp: 103-105                                     3.006 Cl    H                                                                                    ##STR316## IR: 2934, 1592, 1365, 1220, 1059                3.007 Cl    H                                                                                    ##STR317## IR: 2936, 1592, 1493, 1063                      3.008 Cl    H                                                                                    ##STR318## IR: 2935, 1593, 1494, 1063                      3.009 Cl    H                                                                                    ##STR319## IR: 2935, 1593, 1494, 1095, 1063                3.010 Cl    H                                                                                    ##STR320## IR: 2934, 1593, 1494, 1063                      ______________________________________                                    

We claim:
 1. An N-phenyl-tetrahydroindazole of the formula Ia or Ib##STR321## where R¹ is halogen;R² is C₁ -C₃ -alkyl which is substitutedin the 1- or 2-position by a 5- or 6-membered saturated ormonounsaturated heterocycle which contains one sulfur as heteroatom andcan be substituted by from one to four C₁ -C₄ -alkyls, and R₃ is C₃ -C₆-alkynyl or C₁ -C₃ -alkyl which is substituted in the 1- or 2-positionby a 5- or 6-membered saturated or monounsaturated heterocycle whichcontains one sulfur as heteroatom and can be substituted by from one tofour C₁ -C₄ -alkyls.
 2. A herbicidal composition which comprises aneffective amount of an N-(phenyl)-tetrahydroindazole of the formula Iaand/or Ib as set forth in claim 1, and inert additives.
 3. A compound ofthe formula Ia as defined in claim 1, wherein R¹ is Cl and R² is3-tetrahydrothiopyranyl-methyl.
 4. A process for combating the growth ofunwanted plants, wherein the unwanted plants and/or their habitat aretreated with a herbicidally effective amount of anN-(phenyl)-tetrahydroindazole derivative Ia and/or Ib as set forth inclaim 1.